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This tandem cyclization is highly stereoselective, allowing the one\u2010step formation of the bicyclo[5.3.1]undecene system characteristic of taxol. In this work we describe the scope and limitations of such cyclizations.<\/jats:p>","DOI":"10.1002\/chem.200601685","type":"journal-article","created":{"date-parts":[[2007,3,23]],"date-time":"2007-03-23T09:42:39Z","timestamp":1174642959000},"page":"5135-5150","source":"Crossref","is-referenced-by-count":30,"title":["Dienyne Ring\u2010Closing Metathesis Approach for the Construction of Taxosteroids"],"prefix":"10.1002","volume":"13","author":[{"given":"Mar\u00eda\u2005J.","family":"Aldegunde","sequence":"first","affiliation":[]},{"given":"Rebeca","family":"Garc\u00eda\u2010Fandi\u00f1o","sequence":"additional","affiliation":[]},{"given":"Luis","family":"Castedo","sequence":"additional","affiliation":[]},{"given":"Juan\u2005R.","family":"Granja","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2007,6]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"For review see:"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/b204748a"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200200553"},{"key":"e_1_2_6_3_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200200553"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol036062m"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(94)00021-P"},{"key":"e_1_2_6_6_2","unstructured":"\u00a0"},{"key":"e_1_2_6_7_2","volume-title":"Taxol: Science and Applications","year":"1995"},{"key":"e_1_2_6_8_2","volume-title":"Taxane Anticancer Agents: Basic Science and Current Status, ACS Symposium Series 583","year":"1995"},{"key":"e_1_2_6_9_2","first-page":"53","volume":"84","author":"Kingston D. G. I.","year":"2002","journal-title":"Prog. Chem. Org. Nat. Prod."},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1517\/14656566.3.6.755"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/tcr.1008"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1039\/b100070p"},{"key":"e_1_2_6_13_2","first-page":"10","author":"Nicolaou K. C.","year":"1995","journal-title":"Angew. Chem."},{"key":"e_1_2_6_13_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199520791"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1093\/jnci\/82.15.1247"},{"key":"e_1_2_6_15_2","unstructured":"\u00a0"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm0001119"},{"key":"e_1_2_6_17_2","first-page":"129","volume":"16","author":"Wu J. 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S.","year":"2003","journal-title":"Synthesis"},{"key":"e_1_2_6_54_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr980054f"},{"key":"e_1_2_6_55_2","doi-asserted-by":"publisher","DOI":"10.1007\/3-540-69708-X_5"},{"key":"e_1_2_6_56_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo972279g"},{"key":"e_1_2_6_57_2","unstructured":"Our original studies on analogues of the putative transition state of the isomerization of previtamin\u2005D3to vitamin\u2005D3showed that formation of the eight\u2010membered B\u2005ring by RCM is possible only if the constraints introduced by the A\u2005ring are not present."},{"key":"e_1_2_6_58_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol025756c"},{"key":"e_1_2_6_59_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo050568w"},{"key":"e_1_2_6_60_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol0158011"},{"key":"e_1_2_6_61_2","unstructured":"\u00a0"},{"key":"e_1_2_6_62_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00102a062"},{"key":"e_1_2_6_63_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo951648a"},{"key":"e_1_2_6_64_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo972279g"},{"key":"e_1_2_6_65_2","doi-asserted-by":"publisher","DOI":"10.1039\/a900187e"},{"key":"e_1_2_6_66_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(96)00662-4"},{"key":"e_1_2_6_67_2","unstructured":"For convenience steroid numbering is used (see Figure\u20051)."},{"key":"e_1_2_6_68_2","unstructured":"For different reactivities of RCM substrates depending on the relative configuration see:"},{"key":"e_1_2_6_69_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja026401r"},{"key":"e_1_2_6_70_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00112a031"},{"key":"e_1_2_6_71_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(97)00842-9"},{"key":"e_1_2_6_72_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1099-0690(200003)2000:6<975::AID-EJOC975>3.0.CO;2-Q"},{"key":"e_1_2_6_73_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol990909q"},{"key":"e_1_2_6_74_2","unstructured":"For a recent enyne ring\u2010closing metathesis mechanism studies see:"},{"key":"e_1_2_6_75_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja042622g"},{"key":"e_1_2_6_76_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9938231"},{"key":"e_1_2_6_77_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja003582t"},{"key":"e_1_2_6_78_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja010624k"},{"key":"e_1_2_6_79_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0484303"},{"key":"e_1_2_6_80_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0453174"},{"key":"e_1_2_6_81_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00413a016"},{"key":"e_1_2_6_82_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)86410-3"},{"key":"e_1_2_6_83_2","unstructured":"The isolated yields of RCDEYM products11were significantly greater when neutral alumina was used to purify the crude reaction mixture than when silica gel was used; only a 9\u2009% yield of compound11\u2009awas obtained from9\u2009b10\u2009R."},{"key":"e_1_2_6_84_2","unstructured":"After purification on silica gel (see Ref.\u2005[21])."},{"key":"e_1_2_6_85_2","unstructured":"\u00a0"},{"key":"e_1_2_6_86_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(96)00600-4"},{"key":"e_1_2_6_87_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9500038"},{"key":"e_1_2_6_88_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1996-4402"},{"key":"e_1_2_6_89_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4020(96)00414-0"},{"key":"e_1_2_6_90_2","unstructured":"Dienyne9\u2009b10\u2009Swas also prepared to confirm that configuration at C10 is crucial for reactivity and that the 10\u2009Sepimer is not susceptible to RCDEYM. To this end iodide (R)\u20106\u2009bwas prepared from alcohol (R)\u20105\u2009b(see Scheme\u20057) and used to alkylate the potassium kinetic enolate of7 which after allylation of resulting ketone gave a dienyne with spectroscopic characteristics identical to those of the unreactive epimer of9\u2009bobtained from the racemic mixture of6\u2009b. Subjection of this9\u2009b10\u2009Sderivative to RCM conditions with10\u2009aas catalyst afforded13\u2009bin 87\u2009% yield together with a small amount of triene16\u2009b; no11\u2009awas observed (Table\u20051 Entry\u20054)."},{"key":"e_1_2_6_91_2","unstructured":"\u00a0"},{"key":"e_1_2_6_92_2","volume-title":"Modern Aldol Reactions, Vols.\u20051, 2","year":"2004"},{"key":"e_1_2_6_93_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00791a039"},{"key":"e_1_2_6_94_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo01294a030"},{"key":"e_1_2_6_95_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200602780"},{"key":"e_1_2_6_95_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200602780"},{"key":"e_1_2_6_96_2","unstructured":"Note that the 10\u2009Sseries in9\u2009h\u2013jcorresponds to the 10\u2009Rseries in9\u2009a\u2013gdue to the presence of the C19 hydroxy group."},{"key":"e_1_2_6_97_2","unstructured":"It has been proposed that the presence of two nucleophilic hydroxy groups promotes decomposition of the catalyst see:"},{"key":"e_1_2_6_98_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja001415n"},{"key":"e_1_2_6_99_2","doi-asserted-by":"publisher","DOI":"10.1039\/b109651f"},{"key":"e_1_2_6_100_2","unstructured":"All the conditions applied to obtain the diprotected silyl ether failed only affording the monoprotected silyl ether9\u2009j10\u2009S."},{"key":"e_1_2_6_101_2","unstructured":"For some studies of regioselectivity on RCEYM reaction see:"},{"key":"e_1_2_6_102_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja045422d"},{"key":"e_1_2_6_103_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20011119)113:22<4404::AID-ANGE4404>3.0.CO;2-B"},{"key":"e_1_2_6_103_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20011119)40:22<4274::AID-ANIE4274>3.0.CO;2-#"},{"key":"e_1_2_6_104_2","unstructured":"\u00a0"},{"key":"e_1_2_6_105_2","first-page":"10","author":"Leyes G. 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